The present invention relates to novel olefin polymerization catalysts and processes for preparing polypropylenes and propylene block copolymers using the novel catalysts. The present invention also relates to processes for preparing propylene block copolymers using specific olefin polymerization catalysts.
The polypropylene according to the present invention has a high isotacticity. The propylene block copolymer according to the present invention contains a polypropylene component having a high isotacticity and a rubber component having a high intrinsic viscosity [xcex7].
There have been known homopolypropylene generally having excellent rigidity and heat resistance, and propylene block copolymers comprising both polypropylene component and a rubber component and having excellent rigidity and heat resistance as well as excellent impact resistance.
Propylene polymers have also a low specific gravity and can be easily recycled, and therefore, they have been paid much attention with respect to environmental protection and are now desired to be more extensively utilized.
Such propylene polymers are prepared using so-called a Ziegler-Natta catalyst comprising a compound containing a transition metal of Group IV to VI of the periodic table and an organometallic compound containing a metal of Group I to III, and they are widely used.
However, the propylene polymers obtained by the prior art techniques have not always sufficient rigidity and heat resistance in some uses, so that they have limited uses for some purposes.
It is known that the rigidity and the heat resistance of propylene polymers can be further improved by increasing the isotacticity of homopolypropylene or a polypropylene component in a propylene block copolymer, in other words, these properties can be improved by the use of a catalyst capable of providing a high isotacticity for the propylene polymers in the preparation thereof.
However, a polymer of an olefin such as propylene obtained by the use of such a catalyst capable of providing a high isotacticity tends to have a molecular weight higher than that those obtained by using conventional catalysts. Accordingly, it has generally been necessary to add hydrogen as a chain transfer agent in a large amount to the polymerization system in order to regulate a molecular weight and a melt flow rate (MFR) of the resulting polymer. Such a large amount of hydrogen present in the polymerization system, especially when the propylene is per se used as the polymerization solvent, increases the pressure of polymerization system, so that a polymerization reactor may need reinforcing its pressure resistance.
Propylene block copolymers can be prepared by a multi-step polymerization (so-called block copolymerization) process which generally comprises initially polymerizing propylene to form a polypropylene component and then copolymerizing ethylene and an xcex1-olefin to form a rubber component. If this polymerization process is carried out continuously (or in one batch) using the above-mentioned catalyst capable of providing a high isotacticity, a large amount of hydrogen gives rise to a problem. That is, the hydrogen added in the initial step to prepare the polypropylene component remains unreacted in a large amount and then, in the subsequent step, prevents the rubber component from attaining a high molecular weight (instrinsic viscosity [7].
Accordingly, it has been desired that a catalyst system used for the preparation of a polypropylene and a propylene block copolymer be developed, which makes it possible not only to readily regulate the molecular weight and the melt flow rate (MFR) of the resulting polymers using a small amount of hydrogen, but also provide a high isotacticity for the resulting polypropylene and the propylene component of the resulting propylene block copolymer.
Further, it has also been desired that a process for preparing a propylene block copolymer by which the molecular weight and the melt flow rate (MFR) of the resulting copolymer can be easily regulated even with a small amount of hydrogen, isotacticity of a polypropylene component in the resulting copolymer can be heightened, and a molecular weight of a rubber component in the resulting copolymer can also be increased.
The present invention has been made in the light of the foregoing prior art technique, and it is an object of the invention to provide olefin polymerization catalysts by the use of which the molecular weight and the melt flow rate (MFR) of the resulting polypropylene can be easily regulated even with a small amount of hydrogen and highly isotactic polypropylene can be prepared, and to provide processes for preparing polypropylene using said olefin polymerization catalysts.
It is another object of the invention to provide processes for preparing a propylene block copolymer by which the molecular weight and the melt flow rate (MFR) of the resulting copolymer can be easily regulated even with a small amount of hydrogen, isotacticity of the polypropylene component in the resulting copolymer can be heightened, and the molecular weight of the rubber composition in the resulting copolymer can also be increased.
The olefin polymerization catalyst (1) according to the invention is a novel catalyst and formed from:
[I-1] a contact product obtained by contacting:
(A) a solid titanium catalyst component comprising magnesium, titanium, halogen and an electron donor,
(B) an organometallic compound catalyst component, and
(C) an organosilicon compound represented by the following formula (c-i)
RanSi (ORb)4xe2x88x92nxe2x80x83xe2x80x83(c-i) 
xe2x80x83wherein n is 1, 2 or 3; when n is 1, Ra is a secondary or tertiary hydrocarbon group; when n is 2 or 3, at least one of Ra is a secondary or tertiary hydrocarbon group, and plural Ra may be the same or different; Rb is a hydrocarbon group of 1 to 4 carbon atoms; and when 4-n is 2 or 3, plural ORb may be the same or different;
[II-1] (D) a compound having at least two ether linkages spaced by plural atoms; and optionally,
[III] an organometallic compound catalyst component.
The contact product [I-1] in the catalyst (1) may be replaced by a prepolymerized catalyst component [Ia-1] which is obtained by prepolymerizing an olefin of 2 or more carbon atoms in the presence of the catalyst components for forming the contact product [I-1] in such a way that the amount of the prepolymer formed is 0.01 to 2,000 g based on 1 g of the solid titanium catalyst component (A).
The olefin polymerization catalyst (2) according to the invention is formed from:
[I-2] a contact product obtained by contacting:
(A) a solid titanium catalyst component,
(B) an organometallic compound catalyst component, and
(D) compound having at least two ether linkages spaced by plural atoms;
[II-2] (C) an organosilicon compound represented by the above formula (c-i); and optionally,
[III] an organometallic compound catalyst component.
The contact product [I-2] in the catalyst (2) may be replaced by a prepolymerized catalyst component [Ia-2] which is obtained by prepolymerizing an olefin of 2 or more carbon atoms in the presence of the catalyst components for forming the contact product [I-2] in such a way that the amount of the prepolymer formed is 0.01 to 2,000 g based on 1 g of the solid titanium catalyst component (A).
The process for preparing a polypropylene according to the invention comprises polymerizing propylene in the presence of the above-mentioned olefin polymerization catalyst (1) or (2).
The polypropylene prepared by the process of the invention preferably has the following properties:
(i) a boiling heptane-insoluble component is contained in said polypropylene in an amount of not less than 80% by weight,
a pentad isotacticity [Mg] of the boiling heptane-insoluble component determined by the following formula (1) using a 13C-NMR spectrum is not less than 0.97:                               [                      M            5                    ]                =                              [            Pmmmm            ]                                              [              Pw              ]                        -                          2              ⁢                              (                                                      [                                          S                      ⁢                                              xe2x80x83                                            ⁢                      αγ                                        ]                                    +                                      [                                          S                      ⁢                                              xe2x80x83                                            ⁢                                              αδ                        +                                                              ]                                                  )                                      +                          3              ⁡                              [                                  T                  ⁢                                      xe2x80x83                                    ⁢                                      δ                    +                                    ⁢                                      δ                    +                                                  ]                                                                        (        1        )            
wherein
[Pmmmm] is absorption intensity of methyl groups on third propylene units in five propylene unit sequences where the five units are bonded isotactically to each other,
[Pw] is absorption intensity of all methyl groups in propylene units,
[Sxcex1xcex3] is absorption intensity of secondary carbons in a main chain, with the proviso that one of two tertiary carbons nearest to each of said secondary carbons is situated at the xcex1 position and the other is situated at the xcex3 position,
[Sxcex1xcex4+] is absorption intensity of secondary carbons in a main chain, with the proviso that one of two tertiary carbons nearest to each of said secondary carbons is situated at the xcex1 position and the other is situated at the xcex4 or farther position, and
[Txcex4+xcex4+] is absorption intensity of tertiary carbons in a main chain, with the proviso that one of two tertiary carbons nearest to each of said tertiary carbons is situated at the xcex4 or farther position and the other is also situated at the xcex4 or farther position;
a pentad tacticity [M3] of the boiling heptane-insoluble component determined by the following formula (2) using a 13C-NMR spectrum is in the range of 0.0020 to 0.0050:                               [                      M            3                    ]                =                                                                                                  [                    Pmmrm                    ]                                    +                                      [                    Pmrmr                    ]                                    +                                      [                    Pmrrr                    ]                                    +                                      [                    Prmrr                    ]                                    +                                                                                                                          [                    Prmmr                    ]                                    +                                      [                    Prrrr                    ]                                                                                                          [              Pw              ]                        -                          2              ⁢                              (                                                      [                                          S                      ⁢                                              xe2x80x83                                            ⁢                      αγ                                        ]                                    +                                      [                                          S                      ⁢                                              xe2x80x83                                            ⁢                                              αδ                        +                                                              ]                                                  )                                      +                          3              ⁡                              [                                  T                  ⁢                                      xe2x80x83                                    ⁢                                      δ                    +                                    ⁢                                      δ                    +                                                  ]                                                                        (        2        )            
xe2x80x83wherein [Pw], [Sxcex1xcex3], [Sxcex1xcex4+] and [Txcex4+xcex4+] have the meanings as defined in the formula (1),
[Pmmrm] is absorption intensity of methyl groups on third propylene units in five propylene unit sequences represented by ┘ ┘ ┘ ┐ ┐ in which ┘ and ┐ are each a propylene unit,
[Pmrmr] is absorption intensity of methyl groups on third propylene units in five propylene unit sequences represented by ┘ ┘ ┐ ┐ ┘ in which ┘ and ┐ are each a propylene unit,
[Pmrrr] is absorption intensity of methyl groups on third propylene units in five propylene unit sequences represented by ┘ ┘ ┐ ┘ ┐ in which ┘ and ┐ are each a propylene unit,
[Prmrr] is absorption intensity of methyl groups on third propylene units in five propylene unit sequences represented by ┐ ┘ ┘ ┐ ┘ in which ┘ and ┐ are each a propylene unit,
[Prmmr] is absorption intensity of methyl groups on third propylene units in five propylene unit sequences represented by ┘ ┘ ┘ ┐ in which ┘ and ┐ are each a propylene unit,
[Prrrr] is absorption intensity of methyl groups on third propylene units in five propylene unit sequences represented by ┘ ┐ ┘ ┐ ┘ in which ┘ and ┐ are each a propylene unit.
The first process for preparing a propylene block copolymer according to the invention comprises the steps of polymerizing propylene to form a polypropylene component and copolymerizing ethylene and an xcex1-olefin of 3 to 20 carbon atoms to form an ethylene/xcex1-olefin copolymer component, in optional order, wherein both of the polymerizing and copolymerizing steps are carried out in the presence of the above-mentioned olefin polymerization catalyst (1).
The second process for preparing a propylene block copolymer according to the invention comprises steps of polymerizing propylene to form a polypropylene component and copolymerizing ethylene and an xcex1-olefin of 3 to 20 carbon atoms to form an ethylene/xcex1-olefin copolymer component,in optional order, wherein both of the polymerizing and copolymerizing steps are carried out in the presence of the above-mentioned olefin polymerization catalyst (2).
The third process for preparing a propylene block copolymer according to the invention comprises steps of polymerizing propylene to form a polypropylene component and copolymerizing ethylene and an xcex1-olefin of 3 to 20 carbon atoms to form an ethylene/xcex1-olefin copolymer component, in optional order, wherein both of the polymerizing and copolymerizing steps are carried out in the presence of an olefin polymerization catalyst (3) formed from:
[I-3] a contact product obtained by contacting:
(A) a solid titanium catalyst component,
(B) an organometallic compound catalyst component, and optionally,
(D) a compound having at least two ether linkages spaced plural atoms;
[II-3] (D) a compound having at least two ether linkages spaced by plural atoms; and optionally,
[III] an organometallic compound catalyst component.
In the third process for preparing a propylene block copolymer according to the invention, the contact product [I-3] in the catalyst (3) may be replaced by a prepolymerized catalyst component [Ia-3] which is obtained by prepolymerizing an olefin of 2 or more carbon atoms in the presence of the catalyst components for forming the contact product [I-3] in such a way that the amount of the prepolymer formed is 0.01 to 2,000 g based on 1 g of the solid titanium catalyst component (A).
The fourth process for preparing a propylene block copolymer according to the invention comprises steps of polymerizing propylene to form a polypropylene component and copolymerizing ethylene and an xcex1-olefin of 3 to 20 carbon atoms to form an ethylene/xcex1-olefin copolymer component, in optional order, wherein both of the polymerizing and copolymerizing steps are carried out in the presence of an olefin polymerization catalyst (4) formed from:
[I-4] (A-2) a solid titanium catalyst component comprising magnesium, titanium, halogen and (D) a compound having at least two ether linkages spaced by plural atoms;
[II-4] (C) an organosilicon compound represented by the above formula (c-i) and/or (D) a compound having at least two ether linkages spaced by plural atoms; and.
[III] an organometallic compound catalyst component.
In the fourth process for preparing a propylene block copolymer, the olefin polymerization catalyst (4) may be replaced by an olefin polymerization catalyst (4a) formed from:
[Ia-4] a prepolymerized catalyst component obtained by prepolymerizing an olefin of 2 or more carbon atoms in the presence of
(A-2) a solid titanium catalyst component containing magnesium, titanium, halogen and (D) a compound having at least two ether linkages spaced by plural atoms, and
(B) an organometallic compound catalyst component,
in such a way that the amount of the prepolymer formed is 0.01 to 2,000 g based on 1 g of the solid titanium catalyst component (A-2);
[II-4] (C) an organosilicon compound represented by the above formula (c-i) and/or (D) the compound having at least two ether linkages spaced by plural atoms; and optionally,
[III] the organometallic compound catalyst component.
The fifth process for preparing a propylene block copolymer according to the invention comprises steps of polymerizing propylene to form a polypropylene component and copolymerizing ethylene and an xcex1-olefin of 3 to 20 carbon atoms to form an ethylene/xcex1-olefin copolymer component, in an optional order, wherein both of the polymerizing and copolymerizing steps are carried out in the presence of an olefin polymerization catalyst (5a) formed from:
[Ia-5] a prepolymerized catalyst component which is obtained by prepolymerizing an olefin of 2 or more carbon atoms in the presence of
(A) a solid titanium catalyst,
(B) an organometallic compound catalyst component, and
(E) an organosilicon compound represented by the following formula (c-iii)
RnSi(ORxe2x80x2)4xe2x88x92nxe2x80x83xe2x80x83(c-iii) 
wherein R and Rxe2x80x2 are each a hydrocarbon group, and n is a number satisfying the condition of 0 less than n  less than 4;
in such a way that the amount of the prepolymer formed is 0.01 to 2,000 g based on 1 g of the following solid titanium catalyst component (A);
[II-5] (C) an organosilicon compound represented by the above formula (c-i); and optionally,
[III] an organometallic compound catalyst component.
In the present invention, the compound (D) having at least two ether linkages spaced by plural atoms is preferably represented by the following formula: 
wherein n is an integer satisfying the condition of 2xe2x89xa6nxe2x89xa610; R21 to R26 are each a substituent having at least one atom selected from the group consisting of carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon; any optional combination of from R1 to R26, preferably from R1 to R2n, may form together a ring other than a benzene ring; and the main chain of the compound may contain atoms other than carbon.
In the present invention, the organosilicon compound (C) is preferably represented by the following formula (c-ii): 
wherein Ra and Rc are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group or a hydrocarbon group whose carbon adjacent to Si is secondary or tertiary carbon.
According to the processes for preparing a propylene block copolymer of the invention, a propylene block copolymer having the following properties can be prepared.
(i) A boiling heptane-insoluble component in the propylene block copolymer has a pentad isotacticity [Mg], obtained from the above formula (1) using a 13C-NMR spectrum, of not less than 0.97 , and has a pentad tacticity [Mg], obtained from the above formula (2) using a 13C-NMR spectrum, of 0.0020 to 0.0050.
(ii) A 23xc2x0 C. n-decane-soluble component in the propylene block copolymer has an intrinsic viscosity [xcex7], as measured in decahydronaphthalene at 135xc2x0 C., of not less than 2 dl/g.